Semiconductor devices and methods of manufacturing the same

ABSTRACT

A semiconductor device includes a first electrode on a substrate, a selection device pattern, a variable resistance layer pattern, a first protective layer pattern, a second protective layer pattern and a second electrode. The selection device pattern is wider, in a given direction, than the variable resistance layer pattern. The first protective layer pattern is formed on a first pair of opposite sides of the variable resistance layer pattern. The second protective layer pattern is formed on a second pair of opposite of the variable resistance layer pattern. The second electrode is disposed on the variable resistance layer pattern.

PRIORITY STATEMENT

This is a Divisional of U.S. Non-Provisional application Ser. No.14/323,301, filed Jul. 3, 2014, which makes a claim of priority under 35USC §119 to Korean Patent Application No. 10-2013-0136809, filed on Nov.12, 2013 in the Korean Intellectual Property Office (KIPO), the contentsof which are hereby incorporated by reference in their entirety.

BACKGROUND

1. Field

The inventive concept relates to semiconductor devices and methods ofmanufacturing the same. More particularly, the inventive concept relatesto semiconductor devices having vertical memory cell structures andmethods of manufacturing the same.

2. Description of the Related Art

A semiconductor device may include a multi-layered pattern structure. Toform such a structure, different types of layers are formed one atop theother on a substrate, and these layers are patterned by an etchingprocess to form vertical structures constituting memory cells, forexample, of the device. Electrical and mechanical properties of thesemiconductor device may thus depend on how robust the multi-layeredpattern structure is.

SUMMARY

According to an aspect of the inventive concept, there is provided asemiconductor device including a substrate having an upper surface, afirst electrode on the upper surface of the substrate, a selectiondevice pattern on the first electrode, a variable resistance layerpattern on top of the selection device pattern, wherein the variableresistance layer pattern is narrower than the selection device patternin a first direction parallel to the upper surface of the substrate, andthe variable resistance layer pattern has a first pair of sides facingin opposite ways along a second direction, and a second pair of sidesfacing in opposite ways along the first direction, first protectivevertical layers extending along the first sides of the variableresistance layer pattern, respectively, so as to cover the first sidesin the first direction, second protective vertical layers extendingalong the second sides of the variable resistance layer pattern,respectively, so as to cover the second sides in the second direction;and a second electrode on the variable resistance layer pattern.

According to another aspect of the inventive concept, there is provideda semiconductor device including a substrate, a two-dimensional array ofpillars extending upright on the substrate, wherein the pillars arespaced from each other in first and second directions that are parallelto an upper surface of the substrate, and each of the pillars has anupper portion and a lower portion that is wider than the upper portionin at least one of the first and second directions, protective materialthat encases the upper portion of each of the pillars so as to surroundthe variable resistance layer pattern of each of the pillars, andinterlayer insulating material disposed on the substrate and occupyingregions between the pillars including regions between the protectivematerial that encases the upper portions of the pillars, and in whichthe upper portion of each of the pillars includes a variable resistancelayer pattern of material whose resistance can be changed, and theprotective material comprises protective layer patterns that sit atopthe lower portions of the pillars.

According to another aspect of the inventive concept, there is provideda method of manufacturing a semiconductor device, which includes forminga first electrode layer, a selection device layer and a variableresistance layer sequentially on a substrate, selectively etching thevariable resistance layer to form preliminary variable resistance layerpatterns each extending longitudinally in a first direction, forming afirst protective layer along sides of the preliminary variableresistance layer patterns, and a top surface of the selection devicelayer, etching portions of the first protective layer, the selectiondevice layer and the first electrode layer situated between thepreliminary variable resistance layer patterns to form first protectivelayer patterns, preliminary selection device patterns and firstelectrodes, forming a second electrode layer on the preliminary variableresistance layer patterns, selectively etching the second electrodelayer and the preliminary variable resistance layer patterns to formsecond electrodes and variable resistance layer patterns, the secondelectrodes each extending longitudinally in a second direction thatcrosses the first direction, forming a second protective layer alongside surfaces of the second electrodes, sides the variable resistancelayer patterns, and sides of the preliminary selection device patterns,and etching portions of the second protective layer and the preliminaryselection device patterns situated between the variable resistance layerpatterns to form second protective layer patterns and selection devicepatterns.

BRIEF DESCRIPTION OF THE DRAWINGS

The inventive concept will be more clearly understood from the followingdetailed description of the preferred embodiments made in conjunctionwith the accompanying drawings.

FIG. 1 is a perspective view of a semiconductor device in accordancewith the inventive concept;

FIG. 2 shows cross-sectionals of the semiconductor device of FIG. 1 astaken along lines A and B, respectively;

FIGS. 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 and 14 are perspective viewsillustrating a method of manufacturing the semiconductor device of FIG.1;

FIG. 15 is a perspective view of another embodiment of a semiconductordevice in accordance with the inventive concept;

FIG. 16 is a cross-sectional view illustrating the semiconductor deviceof FIG. 15;

FIGS. 17 and 18 are perspective views for use in illustrating a methodof manufacturing the semiconductor device of FIG. 15;

FIG. 19 is a perspective view of still another embodiment of asemiconductor device in accordance with the inventive concept;

FIG. 20 is a cross-sectional view illustrating the semiconductor deviceof FIG. 19; and

FIG. 21 is a perspective view for use in illustrating a method ofmanufacturing the semiconductor device of FIG. 19.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Various embodiments and examples of embodiments of the inventive conceptwill be described more fully hereinafter with reference to theaccompanying drawings. In the drawings, the sizes and relative sizes andshapes of elements, layers and regions, such as implanted regions, shownin section may be exaggerated for clarity. In particular, thecross-sectional illustrations of the semiconductor devices andintermediate structures fabricated during the course of theirmanufacture are schematic. Also, like numerals are used to designatelike elements throughout the drawings.

It will also be understood that when an element or layer is referred toas being on or “connected to” another element or layer, it can bedirectly on or directly connected to the other element or layer orintervening elements or layers may be present. In contrast, when anelement or layer is referred to as being “directly on” or “directlyconnected to” another element or layer, there are no interveningelements or layers present. The same applies to the term “covering”.

It will also be understood that although the terms first, second, third,etc. are used herein to describe various elements, regions, layers,etc., these elements, regions, and/or layers are not limited by theseterms. These terms are only used to distinguish one element, layer orregion from another at the particular place where they are used.

Furthermore, spatially relative terms, such as “upper,” and “lower” areused to describe an element's and/or feature's relationship to anotherelement(s) and/or feature(s) as illustrated in the figures. Thus, thespatially relative terms may apply to orientations in use which differfrom the orientation depicted in the figures. Obviously, though, allsuch spatially relative terms refer to the orientation shown in thedrawings for ease of description and are not necessarily limiting asembodiments according to the inventive concept can assume orientationsdifferent than those illustrated in the drawings when in use. Inaddition, the terms “upper” or “bottom” as used to describe a surfacegenerally refer not only to the orientation depicted in the drawings butmay refer to the fact that the surface is the uppermost or bottommostsurface in the orientation depicted, as would be clear from the drawingsand context of the written description.

Other terminology used herein for the purpose of describing particularexamples or embodiments of the inventive concept is to be taken incontext. For example, the terms “comprises” or “comprising” when used inthis specification specifies the presence of stated features orprocesses but does not preclude the presence or additional features orprocesses. The term “pattern” may be used to refer to one feature in aseries of similar features that have been formed by some patterningprocess and/or may refer collectively to the entire series of featuresformed by the patterning process. Also, at times a pattern that has theform of a layer may be referred to as a “layer”, i.e., the term “layer”does not necessarily refer to a global layer in the device. Also, when afeature is described as “extending” in a particular direction ordirections, it will be understood that those direction correspond to amajor dimension of the feature such as its length as the context andfigures will make clear.

A semiconductor device in accordance with the inventive concept will nowbe described in detail with reference to FIG. 1 and FIG. 2.

The semiconductor memory device may comprise a resistive memory device.The resistive memory device may be a non-volatile memory device in whichthe resistance of a layer is variable to store data. Such a variableresistive memory device may have a high degree of integration comparedto other conventional memory devices, and may be operated with arelatively low amount of power.

Referring to FIGS. 1 and 2, the semiconductor device may include firstelectrodes (referred to hereinafter as first electrode patterns) 103,pillar structures 115, second electrodes (referred to hereinafter assecond electrode patterns) 128 a, first to third protective layerpatterns 120 b, 124 b and 132 a, and a fourth protection layer 136. Thefirst electrode patterns 103, the pillar structures 115 and the secondelectrode patterns 128 a may be disposed one atop the other in theforegoing order. Each pillar structure 115 may include, i.e., may bymade up of at least, a selection device pattern 108 b and a variableresistance layer pattern 112 b.

The first and electrode patterns 103 and 128 a may be spaced apart fromeach other in a vertical direction with respect to a top surface of asubstrate 100. The first and electrode patterns 103 and 128 a may extendperpendicularly to each other. For example, the first electrode pattern103 may have a linear shape and extend longitudinally in a first(1^(ST)) direction. The second electrode pattern 102 a may have a linearshape and extend longitudinally in a second (2^(ND)) directionsubstantially perpendicular to the first direction.

Accordingly, each pillar structure 115 is interposed between respectiveones of the first and second electrode patterns 103 and 128 a. Inparticular, each pillar structure 115 may be located at a point whererespective first and second electrode patterns 103 and 128 a are seen tocross as viewed in plan (which may be referred to hereinafter as a“cross point”).

Thus, a plurality of the pillar structures 115 may be disposed on eachfirst electrode pattern 103 and under each second electrode pattern 128a. Each pillar structure 115 and the portions of the first and secondelectrode patterns 103 and 128 a which are disposed on top and below thepillar structure 115 may provide a respective memory cell.

In the semiconductor device, the resistance of the variable resistancelayer pattern 112 b of the pillar structure 115 may be changed by anelectric field between the first and second electrode patterns 103 and128 a, so that data may be stored in the memory cell. For example, whenthe variable resistance layer pattern 112 b is changed from a highresistance state to a low resistance state, data may be stored. When thevariable resistance layer pattern 112 b is in the high resistance state,e.g., an off-state, a flow of current between the first and secondelectrode patterns 103 and 128 a may be substantially blocked. Incontrast, when the variable resistance layer pattern 112 b is in the lowresistance state, e.g., an on-state, a current may flow between thefirst and second electrode patterns 103 and 128 a. Data may be storedand identified using the above-mentioned characteristics. Thus,operational characteristics of the semiconductor device may be affectedby electrical characteristics of the variable resistance layer pattern112 b.

The first electrode pattern 103 may include a conductive material, e.g.,a metal. The first electrode pattern 103 may have a multi-layered(stacked) structure including a first barrier metal layer pattern 102 aand a first metal layer pattern 104 a. The first barrier metal layerpattern 102 a may include titanium (Ti), titanium nitride (TiN),tantalum (Ta) or tantalum nitride (TaN). The first metal layer pattern104 a may include gold (Au), silver (Ag), copper (Cu), aluminum (Al),titanium aluminum nitride (TiAlN), tungsten (W), tungsten nitride (WN),iridium (Ir), platinum (Pt), palladium (Pd), ruthenium (Ru), zirconium(Zr), rhodium (Rh), nickel (Ni), cobalt (Co), chromium (Cr), tin (Sn),zinc (Zn) or a combination thereof. In one example of this embodiment,the first metal layer pattern 104 a includes a transparent conductivematerial, e.g., indium tin oxide (ITO).

The width of the first electrode pattern 103 is the dimension of thefirst electrode pattern 103 in the second direction. That is, the firstelectrode pattern 103 has side surfaces facing opposite ways in thesecond direction. The second protective layer pattern 124 b may bedisposed on the side surfaces of the first electrode pattern 103.

The selection device pattern 108 b of the pillar structure 115 mayinclude a selective device material which is capable of selecting anelectrical signal. For instance, the selection device pattern 108 b maybe a silicon diode or an oxide diode. The variable resistance layerpattern 112 b may include a material, a resistance of which may bechanged according to the electrical signal applied thereto. At least onemetal layer pattern may be further disposed on lower and upper surfacesof the selection device pattern 108 b, and on lower and upper surfacesof the variable resistance layer pattern 112 b.

In the illustrated example of this embodiment, the pillar structure 115includes a second barrier metal layer pattern 106 b, the selectiondevice pattern 108 b, a second metal layer pattern 110 b, the variableresistance layer pattern 112 b and a third metal layer pattern 114 b,stacked one atop the other in the foregoing order.

The second barrier metal layer pattern 106 b may comprise Ti, TiN, Ta orTaN.

The selection device pattern 108 b may comprise a silicon-basedmaterial, a transition metal compound or a chalcogenide glass. Forexample, the selection device pattern 108 b may have ametal-silicon-metal (MSM) structure.

The second metal layer pattern 110 b may be interposed between theselection device pattern 108 b and the variable resistance layer pattern112 b. The second metal layer pattern 112 b may be formed of Au, Ag, Cu,Al, Ti, TiN, TiAlN, Ta, TaN, W, WN, Ir, Pt, Pd, Ru, Zr, Rh, Ni, Co, Cr,Sn, Zn, ITO or a combination thereof. However, in another example ofthis embodiment, the second metal layer pattern 112 b is omitted.

The variable resistance layer pattern 112 b may comprise a metal oxide,the resistance of which can be changed according to an electric fieldapplied thereto. The variable resistance layer pattern 112 b maycomprise nickel oxide, titanium oxide, tungsten oxide, tantalum oxide,aluminum oxide, zirconium oxide, hafnium oxide, copper oxide, cobaltoxide, iron oxide, vanadium oxide, yttrium oxide, molybdenum oxide,lanthanum oxide, or the like. Alternatively, the variable resistancelayer pattern 112 b may comprise an oxide having a perovskite structure,e.g., praseodymium calcium manganese oxide (PrCaMnO) or doped strontiumtitanium oxide (SrTiO). Still further, the variable resistance layerpattern 112 b may comprise a solid electrolyte, e.g., germaniumtellurium (GeTe) or germanium sulfide (GeS), which may contain adiffusive metal ion, e.g., copper or silver.

The third metal layer pattern 114 b may be disposed on the variableresistance layer pattern 112 b to protect the top surface of thevariable resistance layer pattern 112 b. The third metal layer pattern114 b may comprise Au, Ag, Cu, Al, Ti, TiN, TiAlN, Ta, TaN, W, WN, Ir,Pt, Pd, Ru, Zr, Rh, Ni, Co, Cr, Sn, Zn, ITO or a combination thereof.However, in another example of this embodiment, the third metal layerpattern 114 b is omitted.

Hereinafter, that portion of the pillar structure 115 beneath thevariable resistance layer pattern 112 b will be referred to as a lowerportion of the pillar structure 115, and that portion of the pillarstructure 115 including the variable resistance layer pattern 112 b andany pattern thereon will be referred to as an upper portion of thepillar structure 112 b.

The lower portion of the pillar structure 115 (made up of the secondbarrier metal layer pattern 106 b, the selection device pattern 108 band the second metal layer pattern 110 b in this example) may be wider,in the aforementioned second (2^(ND)) direction, than the upper portionof the pillar structure 115 (made up of the variable resistance layerpattern 112 b and the third metal layer pattern 114 b). Also, the lowerportion of the pillar structure 115 may be wider, in the aforementionedfirst (1^(ST)) direction, than upper portion of the pillar structure115. Accordingly, side surfaces of the pillar structure 115 may havebends in them. Those side surfaces of an element/structure facing inopposite ways in the second direction will be referred to as a firstside surface and a second side surface, respectively. Those sidesurfaces of an element/structure facing opposite ways in the firstdirection will be referred to as a third side surface and a fourth sidesurface, respectively.

The first protective layer pattern 120 b may be formed on the first andsecond side surfaces of the upper portions of the pillar structures 115.The third protective layer pattern 132 a may be formed on the third andfourth side surfaces of the upper portions of the pillar structures 115.Therefore, the first and third protective layer patterns 120 b and 132 amay protect the sides of the variable resistance layer pattern 112 b. Inthe illustrated example of this embodiment, the variable resistancelayer pattern 112 b is surrounded by the first and third protectivelayer patterns 120 b and 132 a.

Outer side surfaces of the first and third protective layer patterns 120b and 132 a may be coplanar with side surfaces of the selection devicepattern 108 b.

The second electrode pattern 128 a may serve as a bit line. The secondelectrode pattern 128 a may have the same width as the upper portion ofthe pillar structure 115 in the first direction.

The second electrode pattern 128 a may comprise a metal. For example,the second electrode pattern 128 a may comprise Au, Ag, Cu, Al, Ti, TiN,TiAlN, Ta, TaN, W, WN, Ir, Pt, Pd, Ru, Zr, Rh, Ni, Co, Cr, Sn, Zn, ITOor a combination thereof.

The third protective layer pattern 132 a and the fourth protective layer136 may also be disposed on the side surfaces of the second electrodepattern 128 a.

The second protective layer pattern 124 b may be disposed on sidesurfaces of the first protective layer pattern 120 b, the second metallayer pattern 110 b, the selection device pattern 108 b and the secondbarrier metal layer pattern 106 b, and on a side surface of the firstelectrode pattern 103 and a top surface of the substrate 100. The fourthprotective layer 136 may be disposed on side surfaces of the thirdprotective layer pattern 132 a, the second metal layer pattern 110 b,the selection device pattern 108 b and the second barrier metal layerpattern 106 b, and on top surfaces of the first and second electrodepatterns 103 and 128 a.

According to examples of the present embodiment as described above, adouble-layered protective pattern covers the side surfaces of the upperportion of the pillar structure 115, whereas a single-layered protectivepattern covers the side surfaces of the lower portion of the pillarstructure 115. In these examples, side surfaces of the variableresistance layer pattern 112 b are surrounded the first, second andthird protective layer patterns 120 b, 124 b and 132 a, and the fourthprotective layer 136.

The first and third protective layer patterns 120 b and 132 a maycomprise protective insulation material. The second protective layerpattern 124 b and the fourth protective layer 136 may also compriseprotective insulation material. For example, the first to thirdprotective layer patterns 120 b, 124 b and 132 a, and the fourthprotective layer 136 may each be formed of a silicon oxide, siliconnitride or a metal oxide alone or in a combination thereof. An exampleof the metal oxide is aluminum oxide. The first to third protectivelayer patterns 120 b, 124 b and 132 a, and the fourth protective layer136 may be formed of substantially the same insulation material or atleast one may be formed of a substantially different insulationmaterials from that of the others.

An insulation layer pattern 126 may be interposed between the adjacentfirst electrode patterns 103 and between the adjacent pillar structures115.

FIGS. 3 to 14 are perspective views illustrating a method ofmanufacturing the semiconductor device of FIG. 1

Referring to FIG. 3, a first barrier metal layer 102 and a first metallayer 104 may be formed on a substrate 100. The first barrier metallayer 102 and the first metal layer 104 may constitute a first electrodelayer.

A second barrier metal layer 106, a selection device layer 108, a secondmetal layer 110, a variable resistance layer 112 and a third metal layer114 may be sequentially formed on the first metal layer 104, i.e., onthe first electrode layer.

Referring to FIG. 4, a first hard mask layer may be formed on the thirdmetal layer 114. The first hard mask layer may comprise a silicon oxide,a spin-on hard mask (SOH) material or silicon oxynitride. Therefore, thefirst hard mask layer may have a multi-layered structure including twoor more of the above materials. In an example of this embodiment, thefirst hard mask layer includes a silicon oxide layer, an SOH layer and asilicon oxynitride layer.

The first hard mask layer may be patterned by, e.g., a photolithographyprocess, to form a first hard mask pattern 118. In the above-mentionedexample of this embodiment, the silicon oxynitride layer and the SOHlayer are removed such that the first hard mask layer pattern 118 is asilicon oxide layer pattern. The first hard mask pattern 118 may includea plurality of linear segments each extending longitudinally in thefirst direction.

Referring to FIG. 5, the third metal layer 114 and the variableresistance layer 112 may be etched using the first hard mask pattern 118as an etching mask to form a third preliminary metal layer pattern 114 aand a preliminary variable resistance layer pattern 112 a. A firsttrench 119 may be defined between the adjacent third preliminary metallayer patterns 114 a and between the adjacent preliminary variableresistance layer patterns 112 a. The etching process may be ananisotropic etching process.

In the illustrated example of this embodiment, the layers under thepreliminary variable resistance layer pattern 112 a are not etched bythis etching process. Thus, the period during which a side surface ofthe preliminary variable resistance layer pattern 112 a is exposed maybe kept to a minimum.

Referring to FIG. 6, a first protective layer 120 may be formed onsurfaces of the third preliminary metal layer pattern 114 a and thepreliminary variable resistance layer pattern 112 a, and along thebottom of the first trench 119. The first protective layer 120 may beformed along the side of the first trench 119 and may not completelyfill the first trench 119. The side surface of the preliminary variableresistance layer pattern 112 a may be protected by the first protectivelayer 120.

The first protective layer 120 may be formed of material that will notbe etched substantially during a subsequent etching process so as not toproduce an etching residue. The first protective layer 120 may be formedof insulation material, e.g., silicon oxide, silicon nitride or a metaloxide, alone or in combination. As mentioned above, aluminum oxide is anexample of an appropriate metal oxide.

Referring to FIG. 7, the first protective layer 120 may be etched fromthe bottom of the first trench 119. Subsequently, the second metal layer110, the selection device layer 108, the second barrier metal layer 106,the first metal layer 104 and the first barrier metal layer 102 may besequentially etched.

As a result, a first barrier metal layer pattern 102 a, a first metallayer pattern 104 a, a second preliminary barrier metal layer pattern106 a, a preliminary selection device pattern 108 a, a secondpreliminary metal layer pattern 110 a may be formed. A first preliminaryprotective layer pattern 120 a may be formed on side surfaces of thepreliminary variable resistance layer pattern 112 a and the thirdpreliminary metal layer pattern 114 a.

A second trench 122 may be formed by the above etching process. Thefirst barrier metal layer pattern 102 a and the first metal layerpattern 104 a may be provided as a first electrode pattern 103. Thefirst electrode pattern 103 may have a linear shape extendinglongitudinally in the first direction.

A first structure including the first electrode pattern 103, the secondpreliminary barrier metal layer pattern 106 a, the preliminary selectiondevice pattern 108 a and the second preliminary metal layer pattern 110a has a wider cross section, in the second direction, than a secondstructure including the preliminary variable resistance layer pattern112 a and the third preliminary metal layer pattern 114 a may have asecond width. The width of the first structure may be equal to the widthof the second structure plus twice the (deposition) thickness of thefirst protective layer 120.

The first protective layer 120 remains on side surfaces of thepreliminary variable resistance layer pattern 112 a while the layersunder the preliminary variable resistance layer pattern 112 a areetched. Accordingly, the side surfaces of the preliminary variableresistance layer pattern 112 a may be prevented from being damaged bythe etching process, so that electrical properties of the preliminaryvariable resistance layer pattern 112 a may be maintained.

The first hard mask pattern 118 may be partially removed by the etchingprocess. Remaining portions of the first hard mask pattern 118 may beremoved by an additional etching process.

Referring to FIG. 8, a second protective layer 124 may be formed onsurfaces of the first preliminary protective layer pattern 120 a, thesecond preliminary metal layer pattern 110 a, the preliminary selectiondevice pattern 108 a, the second preliminary barrier metal layer pattern106 a, the first metal layer pattern 104 a and the first barrier metallayer pattern 102 a, and along the bottom of the second trench 122. Sidesurface of each of these patterns may be protected by the secondprotective layer 124. The second protective layer 124 may be formed ofan insulation material, e.g., silicon oxide, silicon nitride or a metaloxide, alone or in combination. Aluminum oxide is an example of anappropriate metal oxide. The second protective layer 124 may be formedof substantially the same or different insulation material as the firstprotective layer 120.

Referring to FIG. 9, an insulation layer may be formed on the secondprotective layer 124 to fill (overfill) the second trench 122. An upperportion of the insulation layer may be planarized to form an insulationlayer pattern 126 in the second trench 122. A top surface of the thirdpreliminary metal layer pattern 114 a may be exposed by theplanarization process. A second preliminary protective layer pattern 124a may be formed on the side of the second trench 122 by theplanarization process.

Referring to FIG. 10, a fourth metal layer 128 may be formed on thethird preliminary metal layer pattern 114 a, the insulation layerpattern 116, the first preliminary protective layer pattern 120 a andthe second preliminary protective layer pattern 124 a. The fourth metallayer 128 may be transformed into a second electrode pattern by asubsequent process.

For example, a second hard mask pattern 130 may be formed on the fourthmetal layer 128. The second hard mask pattern 130 may have linearsegments extending longitudinally in the second direction substantiallyperpendicular to the first direction.

Referring to FIG. 11, the fourth metal layer 128, the third preliminarymetal layer pattern 114 a and the preliminary variable resistance layerpattern 112 a may be etched using the second hard mask pattern 130 as anetching mask. Accordingly, a second electrode pattern 128 a, a thirdmetal layer pattern 114 b and a variable resistance layer pattern 112 bmay be formed. A third trench 129 may be defined by a space left whenportions of the fourth metal layer 128, the third preliminary metallayer pattern 114 a and the preliminary variable resistance layerpattern 112 a are removed. The third metal layer pattern 114 b and thevariable resistance layer pattern 112 b may have a shape substantiallythat of a pillar. The first preliminary protective layer pattern 120 amay also be etched to form a first protective layer pattern 120 b.

Referring to FIG. 12, a third protective layer 132 may be formed onsurfaces of the second hard mask pattern 130, the second electrodepattern 128 a, the third metal layer pattern 114 b and the variableresistance layer pattern 112 b, and along the bottom of the third trench129. The third protective layer 132 may be formed along the side of thethird trench 129 and may not completely fill the third trench 129. Aside surface of the variable resistance layer pattern 112 b may beprotected by the third protective layer 132.

The third protective layer 132 may be formed of insulation material,e.g., silicon oxide, silicon nitride or a metal oxide, alone or incombination. Aluminum oxide is an example of an appropriate metal oxide.The third protective layer 132 may be formed of insulation materialsubstantially the same as or different from those of the first andsecond protective layers 120 and 124.

Referring to FIG. 13, the third protective layer 132 may be removed fromthe bottom of the third trench 129. Subsequently, the second preliminarymetal layer pattern 110 a, the preliminary selection device pattern 108a and the second preliminary barrier metal layer pattern 106 a may besequentially etched. Accordingly, a second barrier metal layer pattern106 b, a selection device pattern 108 b and a second metal layer pattern110 b may be formed. A third protective layer pattern 132 a may beformed on side surfaces of the second electrode pattern 128 a, the thirdmetal layer pattern 114 b and the variable resistance layer pattern 112b. Thus, the third metal layer pattern 114 b and the variable resistancelayer pattern 112 b may be surrounded by the first and third protectivelayer patterns 120 b and 132 a. A fourth trench 134 may be defined by aspace left when the second preliminary metal layer pattern 110 a, thepreliminary selection device pattern 108 a and the second preliminarybarrier metal layer pattern 106 a are removed. The second preliminaryprotective layer pattern 124 a may also be etched to form a secondprotective layer pattern 124 b.

By the above-described process, a pillar structure 115 may be obtained.A lower portion of the pillar structure 115, including the secondbarrier metal layer pattern 106 b, the selection device pattern 108 band the second metal layer pattern 110 b, may be wider than an upperportion of the pillar structure 115 including the variable resistancelayer pattern 112 b and the third metal layer pattern 114 b, in thefirst direction. The width of the upper portion of the pillar structure115 may be equal to the width of the lower portion of the pillarstructure plus twice the deposition thickness of the third protectivelayer 132, again in the first direction. Outer side surfaces of thefirst and third protective layer patterns 120 b and 132 a may becoplanar with a side surface of the selection device pattern 108 b.

The third protective layer pattern 132 a may be formed on the sidesurface of the variable resistance layer pattern 112 b. Thus, the sidesurface of the variable resistance layer pattern 112 b may be coveredwhile the layers under the variable resistance layer pattern 112 b areetched. Accordingly, the side surface of the variable resistance layerpattern 112 b may be prevented from being damaged by the etchingprocess.

Referring to FIG. 14, a fourth protective layer 136 may be formed onsurfaces of the third protective layer pattern 132 a, the second metallayer pattern 110 b, the selection device pattern 108 b and the secondbarrier metal layer pattern 106 b, and along the bottom of the fourthtrench 134.

Another embodiment of a semiconductor device according to the inventiveconcept will now be described in detail with reference to FIGS. 15 and16.

The semiconductor device may include first electrode patterns 103,pillar structures 115, second electrode patterns 128 a, first to fourthprotective layer patterns 120 b, 142 a, 146 a and 132 b, and fifthprotective layer 136 a.

Each first electrode pattern 103 may extend longitudinally in a first(1^(ST)) direction such the width of the first electrode pattern 103 isthat dimension of the pattern 103 in a second (2^(ND)) directionperpendicular to the first direction. The first electrode pattern 103may include a first barrier metal layer pattern 102 a and a first metallayer pattern 104 a stacked thereon. The third protective layer pattern146 a may be formed on a side surface of the first electrode pattern103.

Each pillar structure 115 may include a second barrier metal layerpattern 106 b, a selection device pattern 108 b, a second metal layerpattern 110 b, a variable resistance layer pattern 112 b and a thirdmetal layer pattern 114 b, stacked one atop the other in the foregoingorder.

The second barrier metal layer pattern 106 b may have a width (dimensionin the second direction) equal to the width of the first electrodepattern 103. The selection device pattern 108 b and the second metallayer pattern 110 b may be narrower, in the second direction, than thebarrier metal layer pattern 106 b. The variable resistance layer pattern112 b and the third metal layer pattern 114 b may be narrower, in thesecond direction, than the selection device pattern 108 b and secondmetal layer pattern 110 b.

The second barrier metal layer pattern 106 b, the selection devicepattern 108 b and the second metal layer pattern 110 b may be wider, inthe first direction, than the variable resistance layer pattern 112 band the third metal layer pattern 114 b.

Thus, the pillar structure 115 may have an upper portion that isnarrower than its lower portion. That is, the pillar structure 115 mayhave bends in its sides at a location where the upper portion and lowerportion meet.

Lateral faces of a structure/element facing oppositely in the seconddirection will be referred to hereinafter as a first side surface and asecond side surface of the structure/element. Lateral faces of astructure/element facing oppositely in the first direction will bereferred to hereinafter as a third side surface and a fourth sidesurface of the structure/element.

The first protective layer pattern 120 b may be disposed on the firstand second side surfaces of the variable resistance layer pattern 112 band the third metal layer pattern 114 b. The fourth protective layerpattern 132 b may be disposed on the third and fourth side surfaces ofthe variable resistance layer pattern 112 b and the third metal layerpattern 114 b. Thus, the first and fourth protective layer patterns 120b and 132 b may surround the variable resistance layer pattern 112 b toprovide protection therefor.

The second protective layer pattern 142 a may be disposed on the firstprotective layer pattern 120 b and on the first and second side surfacesof the selection device pattern 108 b and the second metal layer pattern110 b. The fifth protective layer 136 a may be disposed on the fourthprotective layer pattern 132 b and on the third and fourth side surfacesof the selection device pattern 108 b and the second metal layer pattern110 b. The fifth protective layer 136 a may also be disposed on a topsurface of the second electrode pattern 128 a and an exposed surface ofthe first electrode pattern 103.

The second protective layer pattern 142 a and the fifth protective layer136 a may surround the selection device pattern 108 b to provideprotection therefor.

The third protective layer pattern 146 a may be disposed on the secondprotective layer pattern 142 a, first and second side surfaces of thefirst electrode pattern 103 and an exposed surface of the substrate 100.

The second electrode pattern 128 a may serve as a bit line. The fourthprotective layer pattern 132 b and the fifth protective layer 136 a maybe disposed on the third and fourth side surfaces of the secondelectrode pattern 128 a.

In an example of the embodiment described above, the first, second andthird protective layer patterns 120 b, 142 a and 146 a are disposed onthe first and second side surfaces of the pillar structure 115. Thefourth protective layer pattern 132 b and the fifth protective layer 136a are disposed on the third and fourth side surfaces of the pillarstructure 115. Thus, the side surfaces of the variable resistance layerpattern 112 b and the selection device pattern 108 b can be preventedfrom being damaged during etching processes used to manufacture thedevice.

FIGS. 17 and 18 illustrate key steps in a method of manufacturing thesemiconductor device of FIG. 15.

First, though, processes substantially the same as those illustratedwith reference to FIGS. 3 to 6 may be performed to obtain a structure asshown in FIG. 6.

Referring to FIG. 17, then that portion of the first protective layer120 on the bottom of the first trench 119 may be etched away.

Subsequently, the second metal layer 110 and the selection device layer108 may be etched to form a preliminary selection device pattern 108 aand a second preliminary metal layer pattern 110 a. A first preliminaryprotective layer pattern 120 a may be formed on side surfaces of thepreliminary variable resistance layer pattern 112 a and the thirdpreliminary metal layer pattern 114 a.

A second trench 140 may be formed by the etching process. A side surfaceof the preliminary protective selection device pattern 108 may beexposed by the second trench 140. The second barrier metal layer 106 maybe exposed at the bottom of the second trench 140.

The first protective layer 120 may be formed on side surfaces of thepreliminary variable resistance layer pattern 112 a. Thus, in this case,the side surfaces of the preliminary variable resistance layer pattern112 a are not exposed while the layers under the preliminary variableresistance layer pattern 112 a are etched, such that etching damage tothe variable resistance layer pattern 112 a is prevented.

A second protective layer 142 may be formed on surfaces of the firstpreliminary protective layer pattern 120 a, the second preliminary metallayer pattern 110 a, the preliminary selection device pattern 108 a andthe second barrier metal layer 106 exposed at the bottom of the secondtrench 140. The second protective layer 142 may cover at least a sidesurface of the preliminary selection device pattern 108 a to protect thepreliminary selection device pattern 108 a during a subsequent etchingprocess. The second protective layer 142 may be formed of insulationmaterial, e.g., silicon oxide, silicon nitride or a metal oxide such asaluminum oxide. These may be used alone or in combination. The secondprotective layer 142 may be formed of substantially the same ordifferent insulation material as the first protective layer pattern 120a.

Referring to FIG. 18, the portion of the second protective layer 142 atthe bottom of the second trench 140 may be etched away.

Subsequently, the second barrier metal layer 106, the first metal layer104 and the first barrier metal layer 102 may be sequentially etched toform a first barrier metal layer pattern 102 a, a first metal layerpattern 104 a and a second preliminary barrier metal layer pattern 106a. Also, as a result, a second preliminary protective layer pattern 142a may be formed on the side surfaces of the preliminary selection devicepattern 108 a and the second preliminary metal layer pattern 110 a.

A third trench 144 may also be formed by the etching process. A topsurface of the substrate 100 may be exposed at the bottom of the thirdtrench 144 at this time.

During the etching process, the side surfaces of the preliminaryvariable resistance layer pattern 112 a and the preliminary selectiondevice pattern 108 a may be protected by the first and secondpreliminary protective layer patterns 120 a and 142 a to prevent themfrom being damaged by the etching process.

A third protective layer 146 may be formed on surfaces of the secondpreliminary protective layer pattern 120 a, the second preliminarybarrier metal layer pattern 106 a, the first metal layer pattern 104 a,the first barrier metal layer pattern 102 a and the top surface of thesubstrate 100 exposed by the third trench 144. The third protectivelayer 146 may be formed of substantially the same or differentinsulation material as the first and second protective layer 120 and142.

Processes substantially the same as those illustrated with reference toFIGS. 9 to 14 may then be performed to complete the semiconductor deviceof FIG. 15.

Another embodiment of a semiconductor device according to the inventiveconcept will now be described in detail with reference to FIGS. 19 and20.

The semiconductor device may include first electrode patterns 103,pillar structures 115, second electrode patterns 128 a, first and secondprotective layer patterns 120 b and 124 b, and a third protective layer138.

The first electrode pattern 103 may extend longitudinally in the firstdirection. The first electrode pattern 103 may have a stacked structureincluding a first barrier metal layer pattern 102 a and a first metallayer pattern 104 a. A second protective layer pattern 124 b may beformed on side surfaces of the first electrode pattern 103.

The pillar structure 115 may have a stacked structure including a secondbarrier metal layer pattern 106 b, a selection device pattern 108 b, asecond metal layer pattern 110 b, a variable resistance layer pattern112 b and a third metal layer pattern 114 b.

A lower portion of the pillar structure 115, including the secondbarrier metal layer pattern 106 b, the selection device pattern 108 band the second metal layer pattern 110 b, may be wider, in the seconddirection, than an upper portion of the pillar structure 115 includingthe variable resistance layer pattern 112 b and the third metal layerpattern 114 b.

The patterns constituting the pillar structure 115 may all have the samewidth in the first direction.

Lateral faces of an element/structure facing in opposite ways in thesecond direction may be referred to hereinafter as a first side surfaceand a second side surface of the element/structure. Lateral faces of anelement/structure facing in opposite ways in the first direction may bereferred to hereinafter as a third side surface and a fourth sidesurface of the element/structure.

The first protective layer pattern 120 b may be formed on the first andsecond side surfaces of the variable resistance layer pattern 112 b andthe third metal layer pattern 114 b. The third protective layer 138 maybe formed on the third and fourth side surfaces of the variableresistance layer pattern 112 b and the third metal layer pattern 114 b.Thus, the first protective layer pattern 120 b and the third protectivelayer 138 surround the variable resistance layer pattern 112 b toprovide protection therefor.

The second protective layer pattern 124 b may be formed on a surface ofthe first protective layer pattern 120 b and on the first and secondside surfaces of the selection device pattern 108 b and the second metallayer pattern 110 b. The third protective layer 138 may also be formedon a top surface of the second electrode pattern 128 a and an exposedsurface of the first electrode pattern 103.

The second electrode pattern 128 a may serve as a bit line.

As described above, the first and second protective layer patterns 120 band 124 b may be formed on the first and second side surfaces of thepillar structure 115. The third protective layer 138 may be formed onthe third and fourth side surfaces of the pillar structure 115. A sidesurface of the variable resistance layer pattern 112 b may be protectedby the first protective layer pattern 120 b to prevent etching damagethereto.

The semiconductor device of FIG. 19 may be manufactured by a methodaccording to the inventive concept as follows.

Processes substantially the same as those illustrated with reference toFIGS. 3 to 10 may be performed to obtain a structure as shown in FIG.10.

Referring to FIG. 21, the fourth metal layer 128, the third preliminarymetal layer pattern 114 a, the preliminary variable resistance layerpattern 112 a, the second preliminary metal layer pattern 110 a, thepreliminary selection device pattern 108 a and the second preliminarybarrier metal layer pattern 106 a may be etched using the second hardmask pattern 130 as an etching mask. Accordingly, a second electrodepattern 128 a, a third metal layer pattern 114 b, a variable resistancelayer pattern 112 b, a second metal layer pattern 110 b, a selectiondevice pattern 108 b and a second barrier metal layer pattern 106 b maybe formed.

A pillar structure 115 may be formed by the etching process. A firststructure, including the second barrier metal layer pattern 106 b, theselection device pattern 108 b and the second metal layer pattern 110 b,and may be wider, in the second direction, than a second structureincluding the variable resistance layer pattern 112 b and the thirdmetal layer pattern 114 b. On the other hand, the width of the firststructure, in the first direction, may be equal to that of the secondstructure plus twice the deposition thickness of the first protectivelayer 120.

Referring to FIG. 19 again, the second hard mask pattern 130 may beremoved. A third protective layer 138 may be formed on surfaces of thesecond electrode pattern 128 a, the third metal layer pattern 114 b, thevariable resistance layer pattern 112 b, the second metal layer pattern110 b, the selection device pattern 108 b, the second barrier metallayer pattern 106 b and the first electrode pattern 103 to complete thesemiconductor device of FIG. 19.

According to an aspect of the inventive concept as described above, apattern in a multi-layered pattern structure (stack) of a semiconductordevice, e.g., a resistive memory device, may be protected by at leastone protective layer pattern to reduce the likelihood that the patternwill be damaged when the device is formed using an etching process inwhich layers constituting the stack are etched. Therefore, thesemiconductor device may have a robust mechanical structure and anexcellent electrical property.

According to an example of the inventive concept, the variableresistance layer pattern of the semiconductor device is protected as itis being formed so as to have excellent mechanical and electricalreliability. For example, at least first and second protective layerpatterns of insulation material, capable of suppressing an etchingdamage, collectively surround the variable resistance layer pattern 112b, so that etching damage and/or the attaching of etching residue on thesides of the variable resistance layer pattern 112 b may be preventedduring a patterning process. Thus, the variable resistance layer pattern112 b may have excellent electrical properties.

Therefore, the operational properties of the semiconductor deviceattributed to the variable resistance layer pattern may be excellent.

Finally, embodiments of the inventive concept and examples thereof havebeen described above in detail. The inventive concept may, however, beembodied in many different forms and should not be construed as beinglimited to the embodiments described above. Rather, these embodimentswere described so that this disclosure is thorough and complete, andfully conveys the inventive concept to those skilled in the art. Thus,the true spirit and scope of the inventive concept is not limited by theembodiment and examples described above but by the following claims.

What is claimed is:
 1. A method of manufacturing a semiconductor device,comprising: forming a first electrode layer, a selection device layerand a variable resistance layer sequentially on a substrate; selectivelyetching the variable resistance layer to form preliminary variableresistance layer patterns each extending longitudinally in a firstdirection; forming a first protective layer along sides of thepreliminary variable resistance layer patterns, and a top surface of theselection device layer; etching portions of the first protective layer,the selection device layer and the first electrode layer situatedbetween the preliminary variable resistance layer patterns to form firstprotective layer patterns, preliminary selection device patterns andfirst electrodes; forming a second electrode layer on the preliminaryvariable resistance layer patterns; selectively etching the secondelectrode layer and the preliminary variable resistance layer patternsto form second electrodes and variable resistance layer patterns, thesecond electrodes each extending longitudinally in a second directionthat crosses the first direction; forming a second protective layeralong side surfaces of the second electrodes, sides the variableresistance layer patterns, and sides of the preliminary selection devicepatterns; and etching portions of the second protective layer and thepreliminary selection device patterns situated between the variableresistance layer patterns to form second protective layer patterns andselection device patterns.
 2. The method of claim 1, wherein the firstprotective layer and the second protective layer are formed of siliconnitride or aluminum oxide.
 3. The method of claim 1, further comprising:forming a third protective layer that covers side surfaces of the firstprotective layer pattern, sides of the selection device pattern, andside surfaces of the first electrode coplanar with the side surfaces ofthe first protective layer pattern; and forming a protective layer thatcovers side surfaces of the second protective layer pattern and sides ofthe selection device pattern which are coplanar with the side surfacesof the second protective layer pattern.
 4. The method of claim 1,further comprising forming at least one metal layer on the selectiondevice layer before the variable resistance layer is formed.